Dyestuff of the anthraquinone series



Patented Dec. 26, l933 I it 1,941,0 1;v

THE ANTHRAQUINONE seams Klaus Weinand and Carl Taube, Leverkusen- I; G. We'rk, and Hans Hertlein, Leverkusen- Wiesdori,- Germany,

assignors to General? Aniline Works, Inc., New York, N. -Y., a corporation of Delaware No lilrawing. Application February 4, r 1933. Serial No. 655,252, and in Germany February 8,

. The. present invention relates to a process of, preparing dyestuffs of the anthraquinone. series and to the new products obtainable by said process, a

It is the object of our invention to provide new dyestuffs of the anthraquinone series, possessing the property of dyeing wool or other. animal fibers clear and strong shades, and which are simultaneously valuable dyestufis for the dyeing of vegetable fibers (cotton, viscose etc.) from a neutral or weakly alkaline bath. 7 V

The dyestuffs in question correspondin their,

free form to the probable formula:

wherein a: means one of the numbers 1 or 2 and wherein the nucleus marked I maybe substituted by monovalent substituents, more particularly,.by alkyl groups (methylor ethyl groups, iorf'ex ample) or alkoxy groups (inethoxyethoxy,

propylhydroxy groups etc.). I I v e The new dyestuffs may bepi'epared in various ways. For example, a l-aminoi-halogenanthra-.

quinone-Z-sulfom'c acid is caused to react with a compound or" the formula:--

wherein the littera are tob'e, -Q :ip1aind*aS.-mBIl-. tioned above. The reaction is performed-in. the presence of a suitable solvent at a temperature exceeding about'56-6050. Generally the best results are obtained while applyin a temperature of between about C. and the boiling point of the reaction mixture.

Suitable solvents for performing the reaction are water and organic solvents miscible with water such as pyridine, methylalcohcl, ethylalcohol etc. Water should advantageously be present in all cases.

Likewise it is desirable to add to the reaction mixture a copper catalyst, such as copper, copper oxide or -hydroxide, cuprous oxide, copper chloride, copper sulfate, cuprous bromide, copper acetate or other copper salts. I

Finally, an acid binding agent such as sodium- -or potassium carbonate or -bicarbonates etc. should be added.

7LClairns. (01. 260 -60) Another method of preparing our new dyestuffs is by reacting with 1 molecular proportion of para-phenylene-diamine upon 1* molecular proportion of a 1 aznino-a-halogenanthraquinone-2- sulfonic acid and acylatingthe compound .thus obtained with ahalogenicle or another functional derivative of an acid of the probable formulaz-ewherein the littera are to be explained as mentioned above; 7 The condensation reaction with para-phenylene diamine as well as theacylating reaction are advantageously performed in an aqueous medium and while heating the reaction mixture. Pyridine, sodium acetate or another can i acid binding agent maybe added in the acylating step-of the reaction. I V

The products thus obtainable generally fori'n' dark needles of a bronze-like luster. They dis two hours with 5 formula;-

8"parts of sodium carbonate or -bicarbonate,

' depart of'cuprouschloride anda mixture of 100 parts of water and 50 parts of alcohol. On cooling the dyestufi separates in form of bronzeglittering needles, which dissolve in water with a clear greencoloration and dye cotton from a sodium sulfate bath strong green shades of excell'ent fastness properties, especially to light,

Example 2 7,6 parts .of 1-amino-4-bromoanthraquinone 2-sulfonic acid are heated to boiling for about three hours with 6 parts of monocinnamoyl-paraphenylene diamine, 0.5 part of cuprous chloride and 5 parts of sodium carbonate or -bicarbonate in 200 parts of water. On cooling the new dye-- -2-sulfonic acid are heated to boiling for about parts of the product of the stuff separates in form of dark green needles, which dissolve in water with a bluish-green coloration and dye viscose according to usual methods bluish-green shades of excellent fastness properties, especially to light.

We claim:-

1. The process which comprises heating a compound having in its free form the probable formula:-

( l ialogen with a compound of the probable formula:-

wherein a; stands for one of the numbers 1 or 2 and wherein the nucleus marked I may be substituted by alkylor alkoxy groups, in the presencev of water, a copper catalyst and an acid binding agent at a temperature surmounting about 50-60 C.

2. The process which comprises heating a compound having in its free form the probable formula:-

g halogen I with a compound of the probable formu1a:

wherein :1: stands for one of the numbers 1 or 2 and wherein the nucleus marked I may be substituted by alkyl or alkoxy groups, in the presence of water, a copper catalyst and an acid binding agent at a temperature between about C. and the boiling point of the reaction mixture.

3. The process which comprises reacting upon 1-amino-4-bromoanthraquinone-2-sulfonic acid with the compound of the probable formula:--

in the presence of a copper catalyst, an alkali metal carbonate or bicarbonate and of a mixture of ethylalcohol and water at the boiling point of the reaction mixture.

4. The process which comprises reacting upon 1-amino-4-bromoanthraquinone-2-sulfonic acid with monocinnamoyl-para-phenylenediamine in the presence of water, a copper catalyst and of an alkali metal carbonate or -bicarbonate at the boiling point of the reaction mixture.

5. The products having in their free form the probable general formula:-

said product dissolving in water in forrn-of its alkali metal salts with a green coloration, dyeing cotton from an aqueous bath containing sodium sulfate green shades of excellent fastness to light.

7. The product having in its free form the said product dissolving in water in form of its 7 alkali metal salts with a bluish-green coloration, dyeing viscose bluish-green shades of excellent fastnes's to light. 7

KLAUS WEINAND. CARL TAUBE. HANS HERTLEIN. W 

